WO2020138628A1 - 리튬 이차 전지용 분리막 및 이를 포함하는 리튬 이차 전지 - Google Patents

리튬 이차 전지용 분리막 및 이를 포함하는 리튬 이차 전지 Download PDF

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WO2020138628A1
WO2020138628A1 PCT/KR2019/010130 KR2019010130W WO2020138628A1 WO 2020138628 A1 WO2020138628 A1 WO 2020138628A1 KR 2019010130 W KR2019010130 W KR 2019010130W WO 2020138628 A1 WO2020138628 A1 WO 2020138628A1
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meth
separator
secondary battery
lithium secondary
structural unit
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PCT/KR2019/010130
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English (en)
French (fr)
Korean (ko)
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김용경
김가인
이정윤
최연주
김양섭
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삼성에스디아이 주식회사
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Priority to CN201980085835.2A priority Critical patent/CN113228397B/zh
Priority to US17/296,516 priority patent/US20220029244A1/en
Priority to EP19904249.0A priority patent/EP3905381A4/de
Publication of WO2020138628A1 publication Critical patent/WO2020138628A1/ko

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    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
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    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/42—Acrylic resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
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    • H—ELECTRICITY
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/443—Particulate material
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    • H01—ELECTRIC ELEMENTS
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • It relates to a separator for a lithium secondary battery and a lithium secondary battery comprising the same.
  • the separator for an electrochemical cell is an intermediate film that allows charging and discharging of the battery by continuously maintaining ion conductivity while isolating the positive and negative electrodes in the battery.
  • the separator is mechanically contracted or damaged due to melting characteristics at a low temperature. In this case, a phenomenon in which the battery ignites due to the contact between the anode and the cathode may occur.
  • a method of increasing the thermal resistance of a separator is known by mixing inorganic particles having high thermal resistance with an adhesive organic binder and coating the separator.
  • the existing method cannot sufficiently secure a desired adhesive force and is difficult to apply to a separator having various sizes and shapes.
  • a separator for a lithium secondary battery having high heat resistance and strong adhesion and a lithium secondary battery having improved life characteristics according to the separator.
  • a porous substrate, and a coating layer located on at least one surface of the porous substrate, the coating layer, a first structural unit derived from (meth)acrylamide, and (meth)acrylic acid or (meth)acrylate A heat resistant binder comprising a (meth)acrylic copolymer comprising a structural unit derived from and a second structural unit comprising at least one of (meth)acrylamidosulfonic acid or a structural unit derived from a salt thereof;
  • a lithium secondary battery including a positive electrode, a negative electrode, and a separator for the lithium secondary battery positioned between the positive electrode and the negative electrode is provided.
  • a lithium secondary battery having excellent life characteristics including a separator for a lithium secondary battery having excellent heat resistance and adhesion can be implemented.
  • FIG. 1 is an exploded perspective view of a lithium secondary battery according to an embodiment.
  • FIG. 2 is a schematic diagram of a separator according to an embodiment.
  • FIG 3 is an SEM photograph of a separator coating layer according to an embodiment.
  • FIG. 4 is a schematic diagram of a separator according to another embodiment.
  • FIG. 5 is an SEM photograph of a separator coating layer according to another embodiment.
  • FIG. 6 is a graph showing normal temperature life characteristics for a lithium secondary battery.
  • Example 8 is a graph showing the results of analyzing the OCV drop phenomenon of the lithium secondary battery according to Example 3.
  • hetero' means one or three hetero atoms selected from N, O, S, and P.
  • ком ⁇ онент of these may mean a mixture of components, copolymers, blends, alloys, complexes, reaction products, and the like.
  • (meth)acrylic means acrylic or methacryl.
  • the separator for a lithium secondary battery includes a porous substrate and a coating layer positioned on one or both sides of the porous substrate.
  • the porous substrate has a large number of pores and may be a substrate commonly used in electrochemical devices.
  • Porous substrates include, but are not limited to, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyacetals, polyamides, polyimides, polycarbonates, polyether ether ketones, polyaryl ether ketones, Polyetherimide, polyamideimide, polybenzimidazole, polyethersulfone, polyphenylene oxide, cyclic olefin copolymer, polyphenylene sulfide, polyethylene naphthalate, glass fiber, teflon, and polytetrafluoroethylene It may be any one polymer selected from the group, or a polymer film formed of two or more of these copolymers or mixtures.
  • the porous substrate may be, for example, a polyolefin-based substrate including polyolefin, and the polyolefin-based substrate may have an excellent shutdown function, thus contributing to the improvement of battery safety.
  • the polyolefin-based substrate may be selected from, for example, a polyethylene single film, a polypropylene single film, a polyethylene/polypropylene double film, a polypropylene/polyethylene/polypropylene triple film, and a polyethylene/polypropylene/polyethylene triple film.
  • the polyolefin-based resin may include a non-olefin resin in addition to the olefin resin, or a copolymer of an olefin and a non-olefin monomer.
  • the porous substrate may have a thickness of about 1 ⁇ m to 40 ⁇ m, for example, 1 ⁇ m to 30 ⁇ m, 1 ⁇ m to 20 ⁇ m, 5 ⁇ m to 15 ⁇ m, or 10 ⁇ m to 15 ⁇ m.
  • the separation membrane according to one embodiment may be described with reference to FIGS. 3 to 5.
  • a separation membrane may include a coating layer 30 including a heat-resistant binder (not shown), an adhesive binder 1 and inorganic particles 2.
  • the coating layer may optionally include an organic filler (3).
  • FIG. 3 and 5 are SEM photographs of the separator coating layer
  • FIG. 3 is a SEM photograph of a composition not containing an organic filler
  • FIG. 5 is a SEM photograph of a composition further comprising an organic filler.
  • the heat-resistant binder is a first structural unit derived from (meth)acrylamide, and a structural unit derived from (meth)acrylic acid or (meth)acrylate, and a structural unit derived from (meth)acrylamidosulfonic acid or a salt thereof It may include a (meth) acrylic copolymer comprising a second structural unit containing at least one of.
  • the first structural unit derived from the (meth)acrylamide includes an amide functional group (-NH 2 ) in the structural unit.
  • the -NH 2 functional group can improve the adhesion properties of the porous substrate and the electrode, and by forming a hydrogen bond with the -OH functional group of the inorganic particle, the inorganic particles can be more firmly fixed in the coating layer, and accordingly, the heat resistance of the separator Can strengthen.
  • the structural unit derived from the (meth)acrylic acid or (meth)acrylate included in the second structural unit serves to fix the inorganic particles on the porous substrate, and at the same time, ensures that the coating layer adheres well to the porous substrate and the electrode. It can provide adhesion, and can contribute to improving the heat resistance and air permeability of the separator.
  • the structural unit derived from the (meth)acrylamidosulfonic acid or its salt contained in the second structural unit contains bulky functional groups to reduce the mobility of the copolymer containing it, thereby enhancing the heat resistance of the separator. I can do it.
  • the (meth)acrylic copolymer is a binary copolymer comprising a first structural unit derived from (meth)acrylamide, and a second structural unit derived from (meth)acrylic acid or (meth)acrylate.
  • a binary copolymer comprising a first structural unit derived from (meth)acrylamide, and a second structural unit derived from (meth)acrylamidosulfonic acid or a salt thereof; Or a first structural unit derived from (meth)acrylamide, a structural unit derived from (meth)acrylic acid or (meth)acrylate, and a structural unit derived from (meth)acrylamidosulfonic acid or a salt thereof It may be a ternary copolymer containing two structural units.
  • the first structural unit is 55 mol% to 95 mol% based on 100 mol% of the (meth)acrylic copolymer
  • the second structural unit is 5 mol% based on 100 mol% of the (meth)acrylic copolymer. To 45 mol%.
  • the first structural unit may be included in 75 mol% to 95 mol%, for example, 80 mol% to 95 mol% with respect to 100 mol% of the (meth)acrylic copolymer.
  • the structural unit derived from the (meth)acrylic acid or (meth)acrylate among the second structural units is included in 0 to 40 mol% with respect to 100 mol% of the (meth)acrylic copolymer, and the (meth)acrylic
  • the structural unit derived from amidosulfonic acid or its salt may be included in 0 to 10 mol% based on 100 mol% of the (meth)acrylic copolymer.
  • the structural unit derived from the (meth)acrylamide is included in 80 mol% to 90 mol% based on 100 mol% of the (meth)acrylic copolymer, and derived from the (meth)acrylic acid or (meth)acrylate
  • the structural unit is included in 0 to 10 mol% based on 100 mol% of the (meth)acrylic copolymer
  • the structural unit derived from the (meth)acrylamidosulfonic acid or its salt is 100 mol of the (meth)acrylic copolymer 0 to 10 mol% based on %.
  • the heat resistance and adhesion of the separator may be further improved.
  • the first structural unit derived from the (meth)acrylamide may be represented by, for example, Formula 1 below.
  • R 1 is hydrogen or a C1 to C6 alkyl group.
  • the structural unit derived from the (meth)acrylic acid or (meth)acrylate may be represented by any one of the following Chemical Formula 2, Chemical Formula 3, and combinations thereof.
  • R 2 and R 3 are each independently hydrogen or a C1 to C6 alkyl group, and R 7 is a substituted or unsubstituted C1 to C20 alkyl group.
  • the structural unit derived from (meth)acrylate may be derived from (meth)acrylic acid alkyl ester, (meth)acrylic acid perfluoroalkyl ester and (meth)acrylate having a functional group in the side chain, such as alkyl (meth)acrylate It can be derived from esters.
  • the number of carbon atoms of the alkyl group or perfluoroalkyl group which is bonded to the non-carbonyl oxygen atom of the (meth)acrylic acid alkyl ester or (meth)acrylic acid perfluoroalkyl ester is specifically 1 to 20, more specifically 1 To 10 days, for example, it may be 1 to 5.
  • (meth)acrylic acid alkyl ester having 1 to 5 carbon atoms of an alkyl group or a perfluoroalkyl group that binds to a non-carbonyl oxygen atom, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-acrylate
  • Acrylic acid alkyl esters such as butyl and t-butyl acrylate
  • Acrylic acid-2-(perfluoroalkyl) ethyl such as 2-(perfluorobutyl) ethyl acrylic acid and 2-(perfluoropentyl) ethyl acrylic acid
  • Methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate and t-butyl methacrylate
  • Examples of other (meth)acrylic acid alkyl esters include alkyl groups bound to non-carbonyl oxygen atoms such as n-hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, and isobornyl acrylate.
  • Alkyl ester having 6 to 18 carbon atoms N-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate and cyclohexyl methacrylate
  • Methacrylic acid alkyl esters having 6 to 18 carbon atoms of an alkyl group attached to a non-carbonyl oxygen atom such as; 2-(perfluorohexyl)ethyl acrylate, 2-(perfluorooctyl) ethyl acrylate, 2-(perfluorononyl) ethyl acrylate, 2-(perfluorodecyl) ethyl acrylate, acrylic acid- Perfluoro that binds to non-carbonyl oxygen atoms such as 2-(perfluorododecyl)
  • the structural unit derived from the (meth)acrylic acid or (meth)acrylate may include or include a structural unit represented by Chemical Formula 2 and a structural unit represented by Chemical Formula 3, respectively.
  • the structural unit represented by 2 and the structural unit represented by Chemical Formula 3 may be included in a molar ratio of 10:1 to 1:1, preferably 6:1 to 1:1, more preferably 3:1 to 1:1. have.
  • the structural unit derived from (meth)acrylamidosulfonic acid or a salt thereof may be a structural unit derived from (meth)acrylamidosulfonic acid or (meth)acrylamidosulfonate, and the (meth)acrylamidosulfo Nate may be a pair base of (meth)acrylamidosulfonic acid, (meth)acrylamidosulfonic acid salt, or a derivative thereof.
  • the structural unit derived from the (meth)acrylamidosulfonic acid or (meth)acrylamidosulfonate may be represented by any one of the following Chemical Formula 4, Chemical Formula 5, Chemical Formula 6 and combinations thereof.
  • R 4 , R 5 and R 6 are each independently hydrogen or a C1 to C6 alkyl group
  • L 1 , L 2 , and L 3 are each independently substituted or unsubstituted C1 to C10 alkyl
  • a, b and c are each independently 0 to An integer of 2
  • M is an alkali metal
  • the alkali metal may be, for example, lithium, sodium, potassium, rubidium, or cesium.
  • L 1 , L 2 , and L 3 are each independently a substituted or unsubstituted C1 to C10 alkylene group, and a, b, and c may each be 1.
  • Structural units derived from the (meth)acrylamidosulfonic acid or salts thereof include structural units represented by Chemical Formula 4, structural units represented by Chemical Formula 5, and structural units represented by Chemical Formula 6, respectively, or two or more kinds thereof. It can be included together.
  • the structural unit represented by Chemical Formula 5 may be included, and as another example, the structural unit represented by Chemical Formula 5 and the structural unit represented by Chemical Formula 6 may be included together.
  • the structural unit represented by Chemical Formula 5 and the structural unit represented by Chemical Formula 6 are 10:1 to 1:2, preferably 5 It may be included in a molar ratio of 1:1 to 1:1, more preferably 3:1 to 1:1.
  • the sulfonate group in the structural unit derived from the (meth)acrylamidosulfonic acid or a salt thereof for example, vinyl sulfonic acid, allyl sulfonic acid, styrene sulfonic acid, anethol sulfonic acid, acrylic amidoalkanesulfonic acid, sulfoalkyl (meth)acrylate , Or a functional group derived from a salt thereof.
  • the alkane may be a C1 to C20 alkane, a C1 to C10 alkane, or a C1 to C6 alkane
  • the alkyl may be a C1 to C20 alkyl, a C1 to C10 alkyl, or a C1 to C6 alkyl.
  • the salt means a salt composed of the aforementioned sulfonic acid and an appropriate ion.
  • the ion may be, for example, an alkali metal ion, in which case the salt may be an alkali metal sulfonic acid salt.
  • the acrylamidoalkanesulfonic acid can be, for example, 2-acrylamido-2-methylpropane sulfonic acid
  • the sulfoalkyl (meth)acrylate is, for example, 2-sulfoethyl (meth)acrylate, 3-sulfo Propyl (meth)acrylate, and the like.
  • the (meth)acrylic copolymer may be represented by the following Chemical Formula 7 as an example.
  • R 8 to R 10 are each independently hydrogen or a methyl group
  • R 11 is hydrogen or a C1 to C6 alkyl group
  • L 2 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 To C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 heterocyclic group
  • b is one of integers from 0 to 2
  • M is lithium, sodium, potassium
  • It is an alkali metal, such as rubidium or cesium
  • l, m, and n mean the molar ratio of each unit.
  • l+m+n 1.
  • 0.05 ⁇ (l+n) ⁇ 0.45, 0.55 ⁇ m ⁇ 0.95, and specifically 0 ⁇ l ⁇ 0.4, and 0 ⁇ n ⁇ 0.1 for example, 0.8 ⁇ m ⁇ 0.9, 0 ⁇ l ⁇ 0.1, and 0 ⁇ n ⁇ 0.1.
  • L 2 is a substituted or unsubstituted C1 to C10 alkylene group, and b may be 1.
  • the structural unit substituted with alkali metal (M + ) in the (meth)acrylic copolymer is 50 to 100 mol%, for example 60 to 90 mol%, based on 100 mol% of the total amount of (meth)acrylamidosulfonic acid structural units. Or 70 to 90 mol%.
  • the (meth)acrylic copolymer and the separation membrane containing the same may exhibit excellent adhesion, heat resistance, and oxidation resistance.
  • the (meth)acrylic copolymer may further include other units in addition to the units described above.
  • the (meth)acrylic copolymer is a unit derived from an alkyl (meth)acrylate, a unit derived from a diene system, a unit derived from a styrene system, a unit containing an ester group, a unit containing a carbonate group, or a combination thereof It may further include.
  • the (meth)acrylic copolymer may be in various forms, such as alternating polymers in which the units are alternately distributed, random polymers in random distribution, or graft polymers in which some structural units are grafted.
  • the weight average molecular weight of the (meth)acrylic copolymer may be 350,000 to 970,000, for example, 450,000 to 970,000, or 450,000 to 700,000.
  • the weight-average molecular weight of the (meth)acrylic copolymer satisfies the above range, the (meth)acrylic copolymer and the separation membrane containing the same may exhibit excellent adhesion, heat resistance, and air permeability.
  • the weight average molecular weight may be an average molecular weight in terms of polystyrene measured using gel permeation chromatography.
  • the (meth)acrylic copolymer may be prepared by various known methods such as emulsion polymerization, suspension polymerization, bulk polymerization, solution polymerization, or bulk polymerization.
  • the adhesive binder may be a (meth)acrylic polymer having a core-shell structure, specifically a structural unit derived from (meth)acrylic acid or (meth)acrylate, and a structural unit derived from a monomer containing a polymerizable unsaturated group. have.
  • the core of the adhesive binder includes a structural unit derived from (meth)acrylic acid or (meth)acrylate
  • the shell of the adhesive binder includes a structural unit derived from a monomer containing a polymerizable unsaturated group.
  • the heat-resistant binder comprising the above-mentioned (meth)acrylic copolymer serves to secure heat resistance to reduce the thermal shrinkage at high temperature of the separator, and the adhesive binder secures adhesion to the electrode of the separator It functions. Since the heat resistance and the adhesive force are properties that are in a trade-off relationship with each other, in one embodiment, the heat-resistant binder and the adhesive binder are independently present in the coating layer by further including the adhesive binder together with the heat-resistant binder, thereby allowing heat resistance It is possible to implement a separator excellent in both adhesion and adhesion.
  • the battery stability and life can be improved, and the resistance of the battery can also be improved.
  • Structural units derived from (meth)acrylic acid or (meth)acrylate included in the core of the adhesive binder, as in the heat-resistant binder described above, for example, may be represented by any one of Formula 2, Formula 3, and combinations thereof Can.
  • the monomer containing a polymerizable unsaturated group included in the shell of the adhesive binder may be at least one selected from styrene-based monomers and acid-derived monomers, and combinations thereof.
  • the styrene-based monomer may include at least one aromatic vinyl monomer represented by Formula 8 below.
  • R 12 is hydrogen or a C1 to C6 alkyl group
  • R a to R e are each independently hydrogen or a C1 to C6 alkyl group
  • L 4 is a substituted or unsubstituted C1 to C10 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, or a substituted or unsubstituted C3 to C20 heterocyclic group ,
  • d is one of the integers from 0 to 2
  • the styrene-based monomer may be at least one selected from styrene, as well as methyl styrene, bromo styrene, chloro styrene, and combinations thereof.
  • the acid-derived monomer includes a substituent corresponding to -COOH, and may be at least one selected from itaconic acid, (meth)acrylic acid, and combinations thereof.
  • the adhesive binder may be crosslinked or non-crosslinked.
  • a crosslinking agent may be further added in the polymerization step.
  • the acrylic adhesive binder may have a glass transition temperature of 50°C or higher and 110°C or lower.
  • the adhesive binder may have a predetermined degree of swelling with respect to the electrolyte solution. Specifically, the rate of mass increase (swelling degree) due to the electrolytic solution upon standing at 60° C. for 72 hr may be 50 to 500% or less.
  • the adhesion area of the coating layer in the electrolyte may be increased, but the battery resistance may be increased by reducing adhesion due to swelling and blocking the passage of Li ions.
  • the electrode-separation membrane interface falls during use because adhesion to the electrode does not occur smoothly, thereby causing a decrease in battery reliability due to an increase in side reactions.
  • EC ethylene carbonate
  • DEC diethyl carbonate
  • DMC dimethyl carbonate
  • electrolyte swelling degree can be specifically measured as follows.
  • a polymer is prepared. Then, a film is produced from the prepared polymer. For example, if the polymer is a solid, after drying the polymer at a temperature of 85° C. for 48 hours, the polymer is molded into a film to produce a 0.5 mm thick film. In addition, for example, when the polymer is a solution or dispersion of latex or the like, the solution or dispersion is placed in a polytetrafluoroethylene-made shale and dried at a temperature of 85° C. for 48 hours to produce a film having a thickness of 0.5 mm. do.
  • the film produced as described above is cut into a 1 cm square to obtain a test piece.
  • the weight of this test piece is measured to be W 0 .
  • the test piece was immersed in the electrolyte solution at a temperature of 60°C for 72 hours, and the test piece was taken out of the electrolyte solution.
  • the electrolyte solution on the surface of the removed test piece is wiped off, and the weight W 1 of the test piece after immersion is measured.
  • the type and amount of the monomer for preparing the polymer is appropriate.
  • an electrolyte swelling degree of the polymer may be arbitrarily selected and used.
  • a monomer for example, one type may be used alone, or two or more types may be used in combination at any ratio.
  • aromatic vinyl monomers are preferred. That is, it is preferable that the polymer of the shell contains an aromatic vinyl monomer unit. Moreover, styrene derivatives, such as styrene and styrene sulfonic acid, are more preferable among aromatic vinyl monomers. When an aromatic vinyl monomer is used, it is easy to control the swelling degree of the polymer electrolyte. In addition, the adhesion of the coating layer can be further enhanced.
  • the proportion of aromatic vinyl monomer units in the polymer of the shell is preferably 20% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, especially It is preferably 80% by mass or more, preferably 100% by mass or less, more preferably 99.5% by mass or less, and even more preferably 99% by mass or less. It is easy to control the swelling degree of the electrolyte solution of a shell to the said range by making the ratio of an aromatic vinyl monomer unit into the said range. In addition, it is possible to further increase the adhesion of the coating layer in the electrolytic solution.
  • the shape of the shell is not particularly limited, but the shell is preferably composed of a particulate polymer.
  • the shell is composed of a particulate polymer
  • a plurality of particles constituting the shell in the radial direction of the particles may overlap.
  • the particles constituting the shell do not overlap, and it is preferable that the particles of these polymers constitute the shell portion in a single layer.
  • the average particle diameter of the adhesive binder may be 0.2 ⁇ m to 1.0 ⁇ m, specifically 0.2 ⁇ m to 0.7 ⁇ m, for example, 0.3 ⁇ m to 0.7 ⁇ m or 0.4 ⁇ m to 0.7 ⁇ m.
  • the particle size can be adjusted by controlling the amount of initiator addition, the amount of emulsifier added, the reaction temperature and the stirring speed.
  • the adhesive binder may be included in 1 to 20% by weight based on the total amount of the coating layer, specifically 5 to 20% by weight, for example, 5 to 15% by weight.
  • the adhesive binder is less than the lower limit, the electrode adhesive strength is not developed, and if it exceeds the upper limit, there is a limitation in implementing capacity due to an increase in battery resistance.
  • the coating layer positioned on the separator for a lithium secondary battery according to an embodiment may include inorganic particles in addition to the above-described acrylic heat-resistant binder and adhesive binder.
  • the inorganic particles may prevent the separator from rapidly contracting or deforming due to temperature rise.
  • the inorganic particles may be a ceramic material capable of improving heat resistance, for example, Al 2 O 3 , SiO 2 , TiO 2 , SnO 2 , CeO 2 , MgO, NiO, CaO, GaO, ZnO, ZrO 2 , Y 2 O 3 , SrTiO 3 , BaTiO 3 , Mg(OH) 2 , boehmite, or a combination thereof, but is not limited thereto.
  • the inorganic particles may be spherical, plate-shaped, cubic, or amorphous.
  • the average particle diameter of the inorganic particles may be 0.2 to 1.0 ⁇ m, specifically 0.3 ⁇ m to 1.0 ⁇ m, for example, 0.3 ⁇ m to 0.7 ⁇ m.
  • the average particle diameter of the inorganic particles may be a particle size (D 50 ) at 50% by volume ratio in a cumulative size-distribution curve.
  • the coating layer may include a weight ratio of a heat-resistant binder comprising the (meth)acrylic copolymer: inorganic particles in a weight ratio of 1:20 to 1:40, preferably 1:25 to 1:40, and more preferably May be included in a weight ratio of 1:25 to 1:35.
  • the separator may exhibit excellent heat resistance and air permeability.
  • the weight ratio of the heat-resistant binder and the inorganic particles is less than 1:20, the porosity of the coating layer is lowered by the (meth)acrylic-based copolymer binder, which limits the mobility of Li ions and the moisture adsorption amount of the binder increases, leading to deterioration of battery characteristics.
  • the weight ratio of the heat-resistant binder and the inorganic particles exceeds 1:40, the content of the binder to adhere the inorganic particles is insufficient, so that the heat resistance may be weakened.
  • the separator according to another embodiment may be described with reference to FIGS. 2, 3, and 5.
  • the separation membrane may include a heat-resistant binder (not shown), an adhesive binder 1 and a coating layer 30 ′ comprising inorganic particles 2 in one embodiment.
  • the coating layer includes a heat-resistant layer 20 positioned on a porous substrate, and an adhesive layer 10 positioned on the heat-resistant layer, and the heat-resistant binder and inorganic particles 2 are included in the heat-resistant layer 20 ,
  • the adhesive binder 1 may be included in the adhesive layer 10.
  • the coating layer may optionally include an organic filler (not shown), and the organic filler may be included in at least one layer of a heat-resistant layer and an adhesive layer.
  • the organic filler may be included in the heat-resistant layer or the adhesive layer.
  • FIG. 3 and 5 are SEM photographs of the separator coating layer
  • FIG. 3 is a SEM photograph of a composition not containing an organic filler
  • FIG. 5 is a SEM photograph of a composition further comprising an organic filler.
  • the coating layer may have a thickness of about 1 ⁇ m to 6.5 ⁇ m, for example, 2 ⁇ m to 5 ⁇ m.
  • the thickness of the heat resistant layer is 1 ⁇ m to 5 ⁇ m
  • the thickness of the adhesive layer may be 0.4 ⁇ m to 1.4 ⁇ m
  • the thickness of the heat resistant layer is 1.5 ⁇ m to 3 ⁇ m
  • the thickness of the adhesive layer is 0.5 ⁇ m to 1.0 ⁇ m.
  • the thicknesses of the heat-resistant layer and the adhesive layer are as described above, heat resistance and electrode adhesion characteristics are simultaneously expressed, thereby improving battery safety and reliability. If the thickness of the heat-resistant layer is less than the lower limit, the membrane shrinkage occurs at high temperature to ensure safety, and if it exceeds the upper limit, the heat resistance is excellent, but the performance deteriorates due to an increase in water content and an increase in resistance due to the coating layer. Since the adhesive layer is coated with an adhesive binder in one layer, a thickness similar to the average particle diameter of the adhesive binder is preferable.
  • the heat-resistant layer may further include an organic filler, and the withstand voltage characteristics may be enhanced by further including an organic filler.
  • the average particle diameter of the organic filler may be 120 nm to 500 nm, specifically 120 nm to 400 nm, for example, 150 nm to 300 nm.
  • the coating density of the coating layer is increased, and a contact area through the organic filler between the inorganic particles increases, thereby providing a separator having excellent heat resistance.
  • the volume ratio of the inorganic particles: the adhesive binder and the organic filler may be 33:1 to 1:1, and for example, may be 30:1 to 1:1, or 20:1 to 1:1. For example, it may be 10:1 to 1:1, or 5:1 to 1:1, such as 4:1 to 1:1, or 3:1 to 1:1.
  • the surface roughness of the coating layer is improved, thereby improving the coating uniformity of the coated adhesive layer, thereby improving electrode adhesion, and in addition, the moisture content of the coating layer due to the hydrophobic properties of the inorganic particles.
  • the increase suppression effect can be maximized.
  • the organic filler may be included in an amount of 0.1 to 50% by weight based on the total amount of the coating layer.
  • excellent heat resistance can be secured.
  • the organic filler may be included in 1 to 50% by weight, 3 to 40% by weight, or 1 to 20% by weight relative to the total amount of the coating layer.
  • the organic filler may be included in an amount of 5 to 20% by weight based on the total amount of the coating layer, but is not limited thereto.
  • the organic filler may be at least one organic compound selected from (meth)acrylate-based compounds and derivatives thereof, diallyl phthalate-based compounds and derivatives thereof, polyimide-based compounds and derivatives thereof, copolymers thereof, and mixtures thereof. have.
  • the organic filler can be specifically obtained through the following methods.
  • the organic filler can be obtained by dispersing the (meth)acrylate-based compound in an emulsifying agent, adding a trace amount of a copper sulfate aqueous solution, and then adding an redox polymerization initiator thereto to perform emulsion polymerization.
  • the organic filler can be obtained by polymerizing the diallyl phthalate-based compound in the presence of a water-soluble polymerization initiator.
  • the organic filler can be obtained by reacting an emulsion particle composed of a core portion made of a hydrophobic polymer, a shell portion made of a hydrophilic polymer, and an aldehyde-based compound.
  • the hydrophobic polymer has a glass transition temperature of 20°C or higher and an acetacetyl group
  • the hydrophilic polymer has a water-dispersible functional group.
  • the organic filler may have a highly cross-linked structure.
  • the organic filler may be a polymer material that is an acrylate-based or methacrylate-based polymer or copolymer.
  • the glass transition temperature of the polymer can be controlled by adjusting the monomer ratio of the polymer or copolymer.
  • an acrylate-based or methacrylate-based polymer or copolymer having a glass transition temperature of 30 to 90°C can be used. However, it is not limited thereto.
  • the separator for a lithium secondary battery according to an embodiment may be manufactured by various known methods.
  • a separator for a lithium secondary battery may be formed by applying a composition for forming a coating layer on one side or both sides of a porous substrate and drying it.
  • composition for forming the coating layer may include an initiator and a solvent in addition to a heat-resistant binder, an adhesive binder, and inorganic particles containing the (meth)acrylic copolymer.
  • the initiator may be, for example, a photo initiator, a thermal initiator, or a combination thereof.
  • the photoinitiator may be used when curing by photopolymerization using ultraviolet light or the like.
  • photoinitiator diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2- Acetophenones such as morphine (4-thiomethylphenyl) propan-1-one;
  • Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;
  • the thermal initiator may be used when cured by thermal polymerization.
  • organic peroxide free radical initiators such as diacyl peroxides, peroxy ketals, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxy esters, and peroxydicarbonates can be used.
  • lauroyl peroxide, benzoyl peroxide, cyclohexanone peroxide, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, t-butylhydroper Oxides and the like may be used alone or in combination of two or more.
  • the curing may be performed by photo curing, thermal curing, or a combination thereof.
  • the photo-curing may be performed, for example, by irradiating ultraviolet rays (UV) of 150 nm to 170 nm for 5 seconds to 60 seconds.
  • UV ultraviolet rays
  • the thermal curing may be performed, for example, at a temperature of 60°C to 120°C for 1 hour to 36 hours, for example, at a temperature of 80°C to 100°C for 10 hours to 24 hours.
  • the solvent is not particularly limited as long as it can dissolve or disperse the heat-resistant binder, the adhesive binder, and the inorganic particles.
  • the solvent may be an aqueous solvent including water, alcohol, or a combination thereof, and in this case, there is an advantage of being eco-friendly.
  • the coating may be performed by, for example, spin coating, dip coating, bar coating, die coating, slit coating, roll coating, inkjet printing, etc., but is not limited thereto.
  • the drying may be performed by, for example, drying by natural drying, warm air, hot air or low-humidity air, vacuum drying, far infrared ray, electron beam, or the like, but is not limited thereto.
  • the drying process may be performed at a temperature of 25°C to 120°C, for example.
  • the separator for a lithium secondary battery according to an embodiment has excellent heat resistance.
  • the separation membrane may have a shrinkage rate at a high temperature of less than 10%, or 5% or less.
  • the measured shrinkage in the longitudinal and transverse directions of the separator may be 5% or less, respectively.
  • the separator for a lithium secondary battery according to an embodiment may exhibit excellent air permeability, such as less than 160 sec/100cc ⁇ 1in 2 , 150 sec/100cc ⁇ 1in 2 or less, or 140 sec/100cc ⁇ 1in 2 or less.
  • the air permeability here means the time (seconds) for 100 cc of air to pass through the area of the separator 1 in 2 .
  • the separator for a lithium secondary battery may be manufactured by methods such as lamination and coextrusion in addition to the above-described method.
  • Lithium secondary batteries may be classified into lithium ion batteries, lithium ion polymer batteries, and lithium polymer batteries according to the type of separator and electrolyte used, and may be classified into cylindrical, square, coin, pouch, etc. , It can be divided into bulk type and thin film type according to the size. The structure and manufacturing method of these batteries are well known in the art, so detailed descriptions thereof are omitted.
  • FIG. 1 is an exploded perspective view of a lithium secondary battery according to an embodiment.
  • a lithium secondary battery 100 according to an embodiment is disposed between a negative electrode 112, a positive electrode 114 positioned opposite to the negative electrode 112, a negative electrode 112, and a positive electrode 114.
  • a battery cell including an electrolyte (not shown) impregnating the separator 113 and the cathode 112, the anode 114, and the separator 113, and a battery container 120 and the battery containing the battery cell It includes a sealing member 140 for sealing the container 120.
  • the positive electrode 114 may include a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
  • the positive electrode active material layer may include a positive electrode active material, a binder, and optionally a conductive material.
  • Aluminum, nickel, or the like may be used as the positive electrode current collector, but is not limited thereto.
  • the positive electrode active material a compound capable of reversible intercalation and deintercalation of lithium may be used. Specifically, at least one of cobalt, manganese, nickel, aluminum, iron, or a combination of metals and lithium or a complex phosphorus oxide of lithium may be used.
  • the positive electrode active material may be lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, lithium iron phosphate, or a combination thereof.
  • the binder not only adheres the positive electrode active material particles well to each other, but also serves to adhere the positive electrode active material to the positive electrode current collector, and specific examples include polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, and polyvinyl chloride.
  • Carboxylated polyvinylchloride polyvinylfluoride, ethylene oxide-containing polymer, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, polyvinylidene fluoride, polyethylene, polypropylene, styrene-butadiene rubber, Acrylate-styrene-butadiene rubber, epoxy resin, nylon, and the like, but is not limited thereto. These may be used alone or in combination of two or more.
  • the conductive material is to impart conductivity to the electrode, and examples thereof include natural graphite, artificial graphite, carbon black, carbon fiber, metal powder, and metal fiber, but are not limited thereto. These may be used alone or in combination of two or more.
  • the metal powder and the metal fiber may be metals such as copper, nickel, aluminum, and silver.
  • the negative electrode 112 may include a negative electrode current collector and a negative electrode active material layer formed on the negative electrode current collector.
  • Copper, gold, nickel, copper alloy, and the like may be used as the negative electrode current collector, but is not limited thereto.
  • the negative active material layer may include a negative active material, a binder, and optionally a conductive material.
  • the negative active material includes a material capable of reversibly intercalating and deintercalating lithium ions, a lithium metal, a lithium metal alloy, a material capable of doping and dedoping lithium, a transition metal oxide, or a combination thereof. Can be used.
  • Examples of a material capable of reversibly intercalating and deintercalating the lithium ions include a carbon-based material, and examples thereof include crystalline carbon, amorphous carbon, or a combination thereof.
  • Examples of the crystalline carbon include amorphous, plate-shape, flake, spherical or fibrous natural graphite or artificial graphite.
  • Examples of the amorphous carbon include soft carbon or hard carbon, mesophase pitch carbide, and calcined coke.
  • the lithium metal alloy is lithium and Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Si, Sb, Pb, In, Zn, Ba, Ra, Ge, Al, and Sn. Alloys of the metal of choice can be used.
  • Materials capable of doping and dedoping the lithium include Si, SiO x (0 ⁇ x ⁇ 2), Si-C composite, Si-Y alloy, Sn, SnO 2 , Sn-C composite, and Sn-Y. It can also be used, and it can also be used by mixing at least one of them and SiO 2 .
  • the elements Y are Mg, Ca, Sr, Ba, Ra, Sc, Y, Ti, Zr, Hf, Rf, V, Nb, Ta, Db, Cr, Mo, W, Sg, Tc, Re, Bh, Fe, Pb, Ru, Os, Hs, Rh, Ir, Pd, Pt, Cu, Ag, Au, Zn, Cd, B, Al, Ga, Sn, In, Tl, Ge, P, As, Sb, Bi, S, Se, Te, Po, and combinations thereof.
  • the transition metal oxide include vanadium oxide and lithium vanadium oxide.
  • the type of the binder and the conductive material used in the negative electrode 112 may be the same as the binder and the conductive material used in the positive electrode 114 described above.
  • the positive electrode 114 and the negative electrode 112 may be prepared by mixing each active material and a binder and optionally a conductive material in a solvent to prepare each active material composition, and applying the active material composition to each current collector.
  • the solvent may be N-methylpyrrolidone or the like, but is not limited thereto. Since such an electrode manufacturing method is widely known in the art, detailed description thereof will be omitted.
  • the electrolyte solution includes an organic solvent and a lithium salt.
  • the organic solvent serves as a medium through which ions involved in the electrochemical reaction of the battery can move.
  • a carbonate-based, ester-based, ether-based, ketone-based, alcohol-based or aprotic solvent may be used. Dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methylpropyl carbonate, ethylpropyl carbonate, methylethyl carbonate, ethylene carbonate, propylene carbonate, butylene carbonate, etc.
  • Methyl acetate, ethyl acetate, n-propyl acetate, 1,1-dimethylethyl acetate, methyl propionate, ethyl propionate, ⁇ -butyrolactone, decanolide, valerolactone, mevalonolactone (mevalonolactone), caprolactone, etc. may be used.
  • Dibutyl ether, tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, tetrahydrofuran, and the like may be used as the ether-based solvent, and cyclohexanone may be used as the ketone-based solvent.
  • ethyl alcohol, isopropyl alcohol, etc. may be used as the alcohol-based solvent, and R-CN (R is a C2 to C20 linear, branched or cyclic hydrocarbon group as the aprotic solvent).
  • Amides such as nitriles and dimethylformamide, and dioxolanes such as 1,3-dioxolane, and the like, and sulfolanes.
  • the organic solvent may be used alone or in combination of two or more, and the mixing ratio when used in combination of two or more may be appropriately adjusted according to the desired battery performance.
  • the lithium salt is a material that dissolves in an organic solvent, acts as a source of lithium ions in the battery, enables basic lithium secondary battery operation, and promotes the movement of lithium ions between the positive electrode and the negative electrode.
  • Examples of the lithium salt LiPF 6 , LiBF 4 , LiSbF 6 , LiAsF 6 , LiN(SO 3 C 2 F 5 ) 2 , LiN(CF 3 SO 2 ) 2 , LiC 4 F 9 SO 3 , LiClO 4 , LiAlO 2 , LiAlCl 4 , LiN(C x F 2x+1 SO 2 )(C y F 2y+1 SO 2 )(x and y are natural numbers), LiCl, LiI, LiB(C 2 O 4 ) 2 or combinations thereof However, it is not limited to this.
  • the concentration of the lithium salt can be used within the range of 0.1M to 2.0M.
  • concentration of the lithium salt is within the above range, since the electrolyte has an appropriate conductivity and viscosity, it can exhibit excellent electrolyte performance, and lithium ions can effectively move.
  • the reaction solution was reacted for 12 hours while controlling so that the temperature was stable between 65°C and 70°C. After cooling to room temperature, the pH of the reaction solution is adjusted to 7 to 8 using a 25% aqueous ammonia solution.
  • a poly(acrylic acid-co-acrylamide-co-2-acrylamido-2-methylpropanesulfonic acid) sodium salt was prepared.
  • the molar ratio of acrylic acid, acrylamide, and 2-acrylamido-2-methylpropanesulfonic acid is 10:85:5.
  • the organic/inorganic dispersion liquid having a solid content of 20% having a weight ratio of the heat-resistant binder: inorganic particles: organic filler 1:30:2 was prepared by adding the heat-resistant binder (10% by weight in distilled water) to a water solvent, followed by stirring.
  • SK polyethylene porous substrate
  • the core-shell type adhesive binder (ZEON, PX-SP121, 0.6um, solid content 15%) was diluted with 2% solid content, and then coated with the surface of the heat-resistant layer in a bar coating method at 0.5 ⁇ m, and then at 50° C. for 10 min. During drying, an electrode adhesive layer having a total thickness of 1 ⁇ m was formed to prepare a separator for a lithium secondary battery.
  • Heat-resistant binder A lithium secondary battery separator was prepared in the same manner as in Example 1, except that a heat-resistant layer was formed with a dispersion prepared by mixing inorganic particles (Boehmite, 0.3 ⁇ m) in a weight ratio of 1:35.
  • Heat Resistant Binder Inorganic particles (Boehmite, 0.3 ⁇ m): Organic filler (PMMA, Nippon Shokubai, 150 nm) in a weight ratio of 1: 31: 4, and a dispersion prepared by mixing a heat resistant layer, Example 1 A separator for a lithium secondary battery was manufactured in the same manner as.
  • a separator for a lithium secondary battery was prepared in the same manner as in Example 3, except that a heat-resistant layer coated with a cross-section of 2 ⁇ m was formed instead of coating with 1.5 ⁇ m on both sides of the substrate.
  • Heat-resistant binder Inorganic particles (Boehmite, 0.3 ⁇ m): Organic filler (PMMA, Nippon Shokubai, 150 nm): Mixing the adhesive binder in a weight ratio of 1: 30: 7: 5 to prepare a dispersion, respectively on both sides of the substrate After coating a total thickness of 3 ⁇ m to 1.5 ⁇ m, and then drying at 70° C. for 10 minutes, a separator for a lithium secondary battery was prepared except that a heat-resistant layer was formed.
  • Inorganic particles Boehmite, 0.3 ⁇ m
  • Organic filler PMMA, Nippon Shokubai, 150 nm
  • Adhesive binder on the heat-resistant layer of Example 2 Organic fillers (PMMA, Nippon Shokubai, 150 nm) were mixed at a weight ratio of 1: 2, and the dispersions prepared were coated on both sides with 0.5 ⁇ m, respectively, to a total thickness of 1.0 ⁇ m. After coating, drying was performed at 50° C. for 10 minutes to form an electrode adhesive layer to prepare a separator for a lithium secondary battery.
  • Organic fillers PMMA, Nippon Shokubai, 150 nm
  • a separator for a lithium secondary battery was prepared by coating a double layer of 1.5 ⁇ m on both sides of a substrate using a dip coater to a total thickness of 3 ⁇ m, and then drying it at 40° C. and 50% humidity for 10 minutes to form a heat resistant layer.
  • a separator for a secondary battery was prepared in the same manner as in Example 1, except that inorganic particles (Boehmite) having an average particle diameter of 1.3 ⁇ m were used.
  • a separator for a lithium secondary battery was manufactured in the same manner as in Example 1, except that only a heat-resistant layer was formed without an electrode adhesive layer.
  • a separator for a lithium secondary battery was prepared in the same manner as in Example 3, except that polyvinylpyrrolidone (Basf, K90) was used as the heat-resistant binder.
  • a separator for a lithium secondary battery was prepared in the same manner as in Example 1, except that an average particle diameter of 0.15 ⁇ m (ZEON, PX-SP95) was used as the adhesive binder.
  • a binder prepared by mixing the organic fillers (PMMA, ZEON, PX-A213F) in a weight ratio of 1:10 is applied, In the same manner as 1, a separator for a lithium secondary battery was prepared.
  • LCO A 3000mAh class battery composed of anode and cathode artificial graphite, wound with a separator prepared through an embodiment of the present invention, inserted into an aluminum pouch, and then electrolytic solution LiPF 6 1.2mol EC/PC/PP 2:1:7 composition After the injection, degassing and pouch sealing were performed. The fabricated battery was pressurized for 5 minutes at 70°C so that the electrode and the separator were adhered.
  • Example 1 The cells prepared in Example 1 and Comparative Example 1 were charged at 1.0 C-rate to 4.4 V under constant current/constant voltage (CC/CV) conditions at 25° C., and then cut-off at 0.1 C-rate. , Discharged at 1.0 C-rate to 3.0V.
  • CC/CV constant current/constant voltage
  • the separation membrane according to an embodiment exhibits excellent life characteristics equal to or greater than Comparative Example 1, which does not include an adhesive binder even though the core-shell structure includes an adhesive binder.
  • the modified adhesive binder may block the pores of the microporous separator and lower the air permeability and/or lithium ion transfer ability during the manufacturing process or exposure to high temperatures, but the present invention is carried out.
  • the (meth)acrylic copolymer according to the example it is possible to realize excellent life characteristics by improving the air permeability and/or the lowering of the lithium ion transfer ability.
  • the separation membrane according to an embodiment of the present invention includes a (meth)acrylic copolymer and an adhesive binder having an appropriate particle diameter, thereby ensuring proper electrode/separation membrane binding force while preventing deterioration of air permeability and/or lithium ion transfer ability. have.
  • the separation membrane of the embodiment containing the adhesive binder was measured to have excellent bending strength, whereas when the adhesive binder (Comparative Examples 3 and 6) was not included, there was no adhesive function with the electrode, so the bending strength was not measured. In this case, it is difficult to maintain the shape of the battery by the exterior material (aluminum pouch) during the charging and discharging process, and the battery is warped or the distance between the electrode interfaces becomes uneven, thereby accelerating the formation of by-products such as lithium precipitation, and a problem that the battery thickness increases rapidly. .
  • the battery In the hot box evaluation, the battery is placed in a chamber equipped with a safety device, fixed so that the surface temperature and voltage can be measured, and then the voltage shape is measured while increasing the chamber temperature. When the separator shrinks, a voltage drop may occur, and in severe cases, ignition and explosion may occur. If an event such as ignition/explosion does not occur after leaving the chamber for 1 hour after reaching the target temperature, the hot box evaluation is passed, and when the event occurs, the hot box evaluation is evaluated as fail.
  • FIG. 7 is a graph showing the results of analyzing the OCV drop phenomenon of the lithium secondary battery according to Comparative Example 1
  • Figure 8 is a graph showing the results of analyzing the OCV drop phenomenon of the lithium secondary battery according to Example 3.
  • 150°C heat shrink is to prepare a sample by cutting the separator for a lithium secondary battery to a size of 10 cm x 10 cm, draw a square of size 8 cm x 8 cm on the surface of the sample, sandwich it between paper or alumina powder, and in the oven After standing at 150° C. for 60 minutes, the contraction rate is calculated by measuring the contraction length in the longitudinal/transverse direction.
  • Table 1 shows the results of calculating the shrinkage of each of the longitudinal direction (MD) and the transverse direction (TD) by measuring the dimensions of the side of the rectangle that was drawn and drawn after leaving the sample for 1 hour.
  • the separation membrane according to the embodiment has a heat shrinkage of 5% or less, while the separation membrane according to the comparative example shows that the heat shrinkage of 10% or more and up to 50%.
  • the separation membrane containing the inorganic particles having an average particle size of more than 1.0 ⁇ m has a low coating layer packing density and a smaller contact area between the particles and the particles, so that the binding force between the heat-resistant binder and the inorganic particles decreases. It can be seen that the heat resistance characteristics are significantly lowered.
  • the separator prepared in the Examples comprises a heat-resistant binder comprising inorganic (meth)acrylic copolymers containing specific structural units, inorganic particles, and an adhesive binder, thereby providing excellent substrate adhesion and/or heat resistance, and 10 at 150°C. It shows that the shrinkage rate is less than %, and thus it is possible to realize excellent heat resistance and adhesive properties.

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PCT/KR2019/010130 2018-12-28 2019-08-09 리튬 이차 전지용 분리막 및 이를 포함하는 리튬 이차 전지 WO2020138628A1 (ko)

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CN201980085835.2A CN113228397B (zh) 2018-12-28 2019-08-09 用于锂二次电池的隔板和包括其的锂二次电池
US17/296,516 US20220029244A1 (en) 2018-12-28 2019-08-09 Separator for lithium secondary battery and lithium secondary battery comprising same
EP19904249.0A EP3905381A4 (de) 2018-12-28 2019-08-09 Separator für lithiumsekundärbatterie und lithiumsekundärbatterie damit

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